6.adiabatic Calorimetry

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THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS
6. Adiabatic calorimetry
This HarsBook text has been prepared by a HarsNet working group for use by HarsNet partners. The text has been prepared in good faith but the authors accept no responsibility for the consequences of application of the information contained herein. The HarsNet Thematic network is European Community Project BET2-0572 funded in part by contract number BRRT-CT98-5066. Keywords: Runaway, exotherm, adiabatic calorimetry, thermodynamic, kinetic, phi factor, pressure and temperature measurement, reaction enthalpy, vent sizing. 6.1. Introduction A chemical reaction leads to a runaway when its own heat production rate is faster than heat losses. In most cases, chemical reactions follow an Arrhenius law ( Rate Z exp RT ), where the heat production rate increases exponentially with temperature, whilst the heat removed by the jacket is proportional to the temperature difference between the reactor and jacket ( Rate = UA (Tj - Tr ) ). This is well described by either the theory of Semenov (in which an uniform temperature within the reactor is assumed) or the Frank Kamenetskii theory (which allows for a temperature distribution for an unstirred system). The worst real case and the easiest to understand is when a runaway reaction occurs under adiabatic conditions, that is to say without any heat exchange with the surroundings. (For present purposes the even worse case of loss of cooling with a continued external heat input is ignored.) To study such a case at laboratory scale is not easy because natural cooling changes dramatically with scale. Heat losses are proportional to surface area (i.e. r) and mass to volume (i.e. r3), so heat loss per unit mass is proportional to 1/r (i.e. it reduces dramatically with reactor scale up). Some typical heat loss data are summarised in table 6.1. Note that a one litre Dewar flask has very similar heat loss characteristics to a 12.7 m3 reactor.
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6-1 INDUSTRIAL AND MATERIALS TECHNOLOGIES PROGRAMME OF THE EUROPEAN COMMISSION. PROJECT: BET2-0572 COORDINATION: Prof. Dr. R. Nomen Tel. +34-93-267 20 00 Fax. +34-93-205 62 66 http://www.iqs.url.es/harsnet
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Item test tube Beaker Flask Reactor Reactor Reactor Dewar Reactor
Volume 10 ml 100 ml 1000 ml 2,5 m3 5,0 m3 12,7 m3 1000 ml 25 m3
Cooling time Cooling rate for 1C (C/min) 11 s 5,5 20 s 3 2 min 0,5 21 min 0,047 43 min 0,023 59 min 0,0169 62 min 0,0161 233 min 0,0043
Heat loss* (Watts / kg) 385 210 35 3,29 1,61 1,18 1,13 0,3
Table 6.1. Typical cooling rates and heat loss data. Laboratory and industrial scale equipment, 60C hotter than surroundings (* for an 80% fill level with water) So as to reproduce exactly what occurs during a run-away and learn from laboratory experiments, we can use a technique called adiabatic calorimetry. Ideal adiabatic tests at a PHI factor of 1 give results that are independent of the mass investigated. 6.2. Information required Information that is needed includes thermodynamic and kinetic data that can be applied to real large-scale run-away scenarios (that is to say in the correct range of temperature). With a small number of experiments, and as little calculation as possible, we should be able to determine: adiabatic temperature rise, rate of change of pressure, rate of change of temperature and system characterisation (vapour pressure, gassy or hybrid). We want to answer the following questions : Thermal behaviour. Detected Onset temperature. Induction time. Adiabatic temperature rise. System characterisation. Rate of change of temperature Rate of change of pressure Is there a thermal hazard ? At what temperature is reaction detected ? What is the Time to Maximum Rate (TMR)? What temperature can be reached under adiabatic conditions? Is the pressure rise due to vapour pressure or noncondensable gas production? How many reactions occur? How fast are they? What are the kinetic and Arrhenius parameters? How rapid is the pressure rise? Is it pressure dependent?
So we want to quantify both the potential thermal hazard and the vent size that may be required required to protect a batch or semi-batch reactor vessel.
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6.3. Techniques available Different techniques are used to detect and characterise decomposition of a reaction mixture: some of these such as DSC and DTA are well described in Chapter 3 of HarsBook, so we will now focus on adiabatic and pseudo-adiabatic techniques. A suitable adiabatic calorimeter, for measuring data for the worst case runaway will: a) Be adiabatic Adiabatic conditions can be realised either by using an adiabatic shield (an oven), or by putting the sample into a container having good thermally insulated walls. The second technique was first used with a Dewar flask (silvered and evacuated double-glass wall). Experiments have shown that of all vessels with an insulated wall, Dewar flasks are the best. Better measurements, however, can be obtained by using a combination of the Dewar flask and an adiabatic temperature control system. In most modern adiabatic devices (ARC / Accelerating Rate Calorimeter, VSP / Vent Sizing Package, PHI-TEC, APTAC / Automatic Pressure Tracking Adiabatic Calorimeter.), the experimental set-up is usually able to minimise heat loss from the test cell by maintaining the temperature of the surroundings equal to that of the sample temperature (or to the test cell wall temperature). Test cell volume is typically from 10 to 100 ml, batch introduction of liquid can be performed, threshold detection is about 0.02 C/min for the self-heating rate, and a wide range of temperatures (20400/500C) and pressures (0-100/150 bar) can be used. Another calorimeter (that is difficult to classify) must be mentioned here: with the RSST (Reactive System Screening Tool), the test is non-adiabatic and relies on a constant small heat input to the sample. So the worst-case runway data can be obtained and vent sizing calculations can be performed.
Methanol / Acetic Anhydride
16 175
Pression en bar a
14
Temprature en C Initial Temperatute=20,2C Final Temperature=165,2C Final pressure =14,8 bara
155
12
135
10
115
95
75
55
35
0 0 50 100 150 200
15 250
Time (mn)
Figure 6.1. Adiabatic experiment with low PHI factor; Acetic anhydride / Methanol
Temperature (C)
Pressure (bara)
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b) Have a thermal inertia, f, close to unity. Both the sample and the vessel are under adiabatic conditions, so the heat produced by the sample causes not only an increase in its own temperature but also in the vessel temperature. On the small scale, the thermal mass of the reactor vessel (or cell) is usually a much larger fraction of the total thermal mass than for large scale operation. This can be expressed by the PHI factor: f= Thermal mass of sample and test cell Thermal mass of sample alone [Eq. 6.1]
Phi factors in a large chemical plant are often between 1 and 1.05. The concept of a phi factor can be applied not only to reactors but also to storage vessels, evaporators, distillation columns, etc. It is important to realise that runaway reactions can, and do, occur in these types of equipment as well as in reactors. One must also take into account that static PHI factors can be easily calculated by the previous formula but dynamic or real PHI factors (due to heat transfer limitation through the walls of the vessel) are difficult to evaluate. This is true for both industrial reactor and laboratory test cells. The phi factor is very important. For example, in the case of f = 2, the observed adiabatic temperature rise in the adiabatic instrument will be only half the true adiabatic temperature rise for the chemicals alone. The consequence is that the experiment is not performed over the correct range of temperature; failure to detect consecutive reactions and gross underestimates of the rates of reaction may result. Thus it is better to work with f close to unity and normally in the range 1.05 to 1.1. In the case of experimentation at a high Phi factor, data correction is required before vent sizing calculations and kinetic or thermodynamic evaluations can be made. This may involve data extrapolation over a large range of temperature and this is not recommended. To achieve the objective of a low phi factor, the test cell mass must be as low as possible. As a result it will not be very strong, yet it must be able to be used at high pressure. It is therefore necessary to match or balance the pressure outside the test cell to that in the head space above the sample so as to avoid rupture of the cell. This method of operation is used in the cases of the VSP, PHI TEC and APTAC equipment. c) Work with a Heat, Wait and Search routine. In order to obtain a better sensitivity for runaway detection, a Heat, Wait and Search routine should be performed. This procedure consists of Heating the sample to the required temperature, Waiting for stabilisation and then Searching, to detect if any exothermic phenomenon is occurring. If no exotherm is detected, the sample is Heated to a new temperature and the process repeated. This continues step by step until a runaway is detected or a maximum temperature is reached. This routine can be applied flexibly to allow isothermal or ramped temperature modes to be used. Autocatalytic behaviour can be studied.
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120
100
Temprature en C
80
Search Heat Wait Search
60
Search Heat Wait
Heat Wait
40
20
0 0 2000 4000 6000 8000 10000 12000 14000 16000
Initialisation
Search
Search
Wait
temps en s
Figure 6.2. Heat-Wait-Search experiment d) Work at conditions close to the industrial ones Accurate results can be obtained only if the user takes care to perform laboratory experiments analogous to industrial conditions. That is to say using a glass test cell when reactions are performing in a glass reactor in order to avoid catalysis, under nitrogen or air, with good agitation, etc... All industrial conditions may be difficult to reproduce at the laboratory scale but keep in mind that one must work as close as possible to them
Comparison Laboratory adiabatic calorimeter / Pilot scale test (350 litres)
140 130 5 120 110 100 Pilot Vapor Temperature 90 80 70 60 0 50 40 0 200 400 600 Time (s) 800 1000 1200 -1 -3.2 Pilot Liquide Temperature LaboratoryTemperature LN (dT/dt) (C/min) Temperature (C) Relief Temperature in pilot experiment 4 6
Search
Heat Wait
Heat Wait
Track
Cool
Comparison Kinetic Adiabatic calorimeter / Pilot plant experiment
3 Laboratory test Pilot test 2
-3
-2.8
-2.6 -1000 / T (K)
-2.4
-2.2
-2
Figure 6.3. Comparison between a laboratory adiabatic experiment and a pilot plant experiment
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a) Dewar Flask.
6.4. Comparison of techniques and relative merit
Typically, a calorimeter comprises a 1-litre stainless steel Dewar inside an oven that is programmed to follow the temperature inside the Dewar to achieve adiabaticity. But you can also use a cheap domestic item (sold by Thermos or Camping Gaz) in which the original plastic cap is replaced by welding a thread to hold a cap equipped with thermocouples, a pressure gauge (and an optional agitator, rupture disk and blow-down valve). Dewar calorimeters have a good sensitivity because of the large amount of chemicals used, and the mixing can be very good with mechanical agitation. The f factor is typically 1.1 for a stainless steel vessel, and 1.8 for a glass one. Only the stainless steel vessel can be used for pressure experiments and these must be performed in a laboratory equipped with blast cells from which personnel are excluded during experiments. The results are comparable to those from VSP or PHI TEC but maximum pressures are limited to the order of 25 bar (as opposed to ~140 bar) and maximum temperature tracking rates are ~ 20 to 30omin-1. The Dewar flask can be recommended for reactions with a moderate final pressure b) ARC. Accelerating Rate Calorimeter. The sample is placed in a small bomb and heated until the initial runaway temperature. The external heater then tracks the sample temperature to ensure adiabaticity (in fact 3 different modes can be used, Heat Wait and Search, isothermal and Ramp Wait Search procedures). Due to the heat capacity of the bomb (to avoid its rupture), the f factor for the ARC is high: typically 2 or 4 (extreme values are 1.2 to 9). In some cases, this can allow a better understanding of complex kinetics. These f factor values prohibit the use of data directly for vent sizing and, as we said before, can lead to wrong determination of the adiabatic temperature rise. ARC data needs careful correction (see use of data). Also the thermocouple is located outside the cell and this can lead to wrong interpretation of data in the case of a viscous solution or very fast reaction. Runaway detection is very good, and a low onset temperature is detected; sensitivity can be down to 0.02C/min. No mixing and no remote feeding is possible: the use of metal cells may present chemical compatibility problems in some circumstances. Kinetic results can be obtained only if the experiment goes to completion (no cell rupture) so it is recommended to use techniques such as DSC, DTA, RSST or an Autoclave to define experiments. The ARC is the most commonly used adiabatic equipment for thermal run-away detection; recent improvements in the software have been made. The ARC is very good for detecting runaways, and understanding decomposition, but correction of data is necessary for scale-up. The latter requires some modelling or assumptions about the reaction kinetics. The equipment has physical limits (feeding, mixing, etc.)
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c) VSP PHITEC APTAC The concept is the same for these three different bench scale calorimeters. Low thermal inertia is achieved by using a very thin-walled test cell within a larger pressure containment vessel. The weakness of the test cell is compensated for by maintaining the pressure in the containment vessel essentially equal to that in the test cell so as to prevent cell rupture. A pressure control system which can either add or vent nitrogen from the containment vessel is provided for this purpose. These calorimeters have a very low f factor, good exotherm detection sensitivity (of the order of 0.02C/min) and a wide range of both temperature (up to 500C) and pressure (up to 200 bar). The Heat Wait Search routine, relatively good mixing, open or closed cell tests and remote feeding possibilities are all features. These devices give very accurate and useful data to characterise runaways and to use for designing reactor venting systems. Nevertheless, a high level of expertise is required to operate the equipment and to interpret results. One must ensure good calibration of the different sensors for heat loss compensation (which is both temperature and pressure dependent) and oven regulation. One should also try to avoid any cell rupture. Other screening devices with pressure information may need to be used for initial tests. Testing using these types of calorimeter is expensive and time-consuming. These types of calorimeter offer perhaps the best technique to obtain very accurate data, but they can only be used as a complement to other tests in a well-equipped laboratory. Detailed adiabatic testing is often carried out at a fairly late stage of process development. d) RSST Reactive System Screening Tool As its name implies, this calorimeter is useful for screening purposes and is smaller and than those described above. The test is non-adiabatic, but relies on a constant small heat input to the sample which compensates for heat losses and which raises the sample temperature. Tests are performed in a 10 ml open cell test with low f factor (1.05) and magnetic stirrer. Nitrogen pressure in the containment vessel is used to suppress boiling from the sample: feeding is possible. The new version called ARSST can work with the Heat Wait Search procedure, although the earlier equipment only works with a constant heating ramp (as is often used in DSC). Temperature and pressure information are obtained and round robin tests showed good agreement between RSST and VSP experiments. When used with special formulae, the results should be safe (but might be over conservative) for relief system sizing. Due to its design, RSST can easily be used for screening up to 500C. All spare parts can be changed for each test. Given that adiabatic conditions are difficult to produce and that so many details may influence the heat rate and gas generation rate data, the results obtained from RSST experiments seem surprisingly good. RSST is a useful tool for screening, but data must be used very carefully, and in some cases, genuine adiabatic tests are required.
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6.5 How to use data
To use data from adiabatic experiments, one must be very careful about: - How the data was obtained (type of calorimeter, adiabaticity, acquisition rate etc.) - How the data was reduced, smoothed or processed (to avoid noise but to keep vital features and to generate derived data) - Problems occurring during the experiment (lack of adiabaticity, leaks between the test cell and containment vessel, cell rupture, oven regulation problems, etc.) A high level of expertise is needed to interpret the results and it is of course better when the same person can perform the experiment and interpret results. Onset temperature determination must be expressed with the experimental conditions used to determine it and always quoted together with the threshold detection rate. For kinetic and thermodynamic results, two cases must be described: In both cases it is assumed that the temperature rise observed is proportional to the degree of conversion and that the rate constant depends on the temperature according to the Arrehnius law. 6.5.1. In the case of a low f factor (< 1.1) a) Thermodynamics The adiabatic increase of temperature can directly be deduced from experimental data: DTad = (Tend - Tonset ) [Eq. 6.2]
From this value, it is possible to estimate global decomposition enthalpy (assuming a mean value for the specific heat of the reaction mixture): - DH dec = m c v DTad b) Kinetics Thermal conversion can be expressed by a: a = [Eq. 6.3]
(Tend - Tonset )
(T - Tonset )
So the classic kinetic expression: v = f (T ) g (a ) expressed assuming Arrhenius dependency

da = Z e RT g(a ) can be written in the case of a unique nth order reaction : dt -E
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-E -E
dT Z n n = Z e RT (1 - a ) = e RT (Tend - T ) n -1 dt (DTad )
[Eq.6.4]
Or rewritten as
Z dT - E + n ln (Tend - T ) ln = ln n -1 dt (DTad ) RT
[Eq. 6.5]
1 dT So, when performing multilinear regression with ln as dependant variable and and RT dt
ln (Tend - T ) as independent variables, one can determine E (activation energy) and n (order of reaction) As a final step, the Time to Maximum Rate (TMR) can be calculated:
TMR = E 2nR
4 n R Tend - 1 1+ E
[Eq. 6.6]
Other methods can be used to determine kinetic parameters, assuming first or second order reactions (or more complex kinetics) and useful information can also be obtained for autocatalytic systems.
6.5.2. In the case of a high f factor (> 1.1)
a) Thermodynamics The adiabatic increase of temperature can be calculated from the experimental temperatures and the f factor :
DTad ,ideal = f (Tend - Tonset )
[Eq. 6.7]
b) Kinetics In relation to the ARC a method (proposed by D.I. Townsend and J.C. Tou) for phi factor correction for exotherm data near the onset temperature, or for zero order kinetics, is: dT dT = f dt ideal dt mesl [Eq. 6.8]
A method was proposed to correct the whole heat rate curve, but this method is not generally satisfactory.
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It is necessary to be familiar with the theory by Townsend and Tou to have a good understanding of the correction methods. When the experimental heat rate data must be corrected to adiabatic conditions at a temperature far from the onset temperature, and when the reaction is not zero order, a method was proposed by Fisher, after Huff. In this method, the onset temperature is first re-calculated: 1 1 R = + ln T0 To, mes E [Eq. 6.9]
This correction takes into account the fact that for a given onset detection sensitivity of the experimental device, the onset temperature would have been lower if the f factor was 1. Then an adjusted temperature Ta for f=1 is calculated: Ta = T0 + f (Tmes - T0 ) The corrected heat rate for f=1 is obtained from the measured heat rate by :
E dT = f EXP dt F =1 R 1 1 dT T - T dt F >1 a mes
[Eq. 6.10]
[Eq. 6.11]
Other methods are available to correct data obtained with a high f factor, but for each one you need kinetic information (a good kinetic fit to the data and an activation energy) to recalculate the temperature heat rates for phi = 1.
6.5.3. Pressure information
Kinetic modelling is also possible from pressure measurements after correction for the initial presence of any inert gases (assuming the ideal gas law). For high vapour pressure systems, the corrected pressure when plotted on a log scale is often a linear function of reciprocal absolute temperature (i.e. an Antoine type relationship is followed). A deviation from what was initially a vapour pressure type curve may indicate the production of non-condensable gases. Pressure increases resulting from production of non-condensable gases can be expressed as a function of conversion. The kinetics of both temperature and pressure development can be compared to validate reaction details (e.g. order of reaction, single/multiple reactions, etc.)
6.6. How to use data for vent sizing
At a final step, a reactor pressure relief vent may need to be designed to protect an industrial installation in the event of a thermal runaway. A good safety vent must be designed to avoid
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increase of pressure above the maximum allowable pressure of the reactor. In order to predict the two phase mass flux, pressure and temperature during venting, one needs to consider the following equations: overall mass balance, gas component balance, energy balance and equation of state. Data from adiabatic calorimetry allows determination of: System classification; Vapour pressure (pressure developed as a consequence of increasing vapour pressure), Gassy (pressure developed as a consequence of non condensable gas production) or Hybrid (a combination of the two). Rate of heat generation. dT/dt and dP/dt under real adiabatic conditions. To be used these values must be obtained with a very low phi factor (close to unity). Type of discharge from the vent. Foamy, bubbly, churn turbulent or all gas/vapour. This determination at the laboratory scale is topic of ongoing discussion. Extrapolation to the large scale requires care and is subject to some uncertainty. Examples of equations used for vent sizing for a vapour system Leung, J.C. (1986):
A ideal = m0q
1 2 v h fg + (cpf DT )12 G m0 v fg 2
[Eq. 6.12]
A ideal =
m 0q
1 2 1 v dP + (c pf DT ) 2 G T s m dT 0 2
[Eq. 6.13]
A = 1.510 -5
m 1 dT (T = Ts ) F Ps dt manip1
[Eq. 6.14]
This equation can only be used with RSST values Examples of equations used for vent sizing for a Gassy system :
A ideal = m r V0bm Pm V0 G a 0 mr
[Eq. 6.15]
Leung, J.C. (1987)

A ideal = m r V0bm Pm G a V1 + bm V0 Dt (1 - x1 ) 0
[Eq. 6.16]
Singh, J (1994)
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Vent sizing must be done with care: account must be taken of the experimental conditions at which raw data were obtained and extrapolability of this raw data. (Extensive extrapolation without additional verification should never be made). The worst credible maloperation must be defined and the range of validity of formula checked. Actually for a complex system (e.g. in which the physical properties of the chemicals involved are not well known) results from vent sizing calculations must be taken as indicative. A safety factor may be required so as not to underestimate the correct vent size: (this factor is already included in simplified formula given above).
6.7. Tabulated comparison
Apparatus Carius tube Dewar flask RSST ARC VSP PHITEC APTAC
Adiabatic
Pressure Low f factor compensati on

X X X X
Heat Wait Search

X X X
Closed cell test

X X X
Easy to Stirring use

X X X X X X X X
X X X
6.8. Nomenclature :
Z : pre-exponential factor E : Activation energy R : Ideal gas constant Tr : Reaction temperature Tj : Jacket temperature DTad : Adiabatic temperature rise Tend : Final temperature of the experiment DHdec : Decomposition enthalpy mr : reaction mass Cv : specific heat at constant volume a : Thermal conversion n : order of reaction Tideal : Temperature in real adiabatic condition Tmes : Temperature measured during experiment To = Tonset = Initial temperature of a run away detected by the instrument
Vent sizing formula : M0 : Initial mass (batch) Q : Specific heat release rate G : Mass flux v : Specific volume
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hfg : Latent heat of vaporisation vfg : Specific volume difference between vapour and liquid cpf : Liquid specific heat at constant pressure DT : over-temperature corresponding to over pressure A : Vent area F : Flow reduction factor Ps : Set pressure dT/dt : Temperature rise rate, self-heat rate Ts : Set temperature dP/dt : pressure rise rate m = mr : Mass of reactant bm : Maximum rate of pressure rise per unit mass of reactant Pm : Turnaround pressure a0 : Void fraction x1 : Mass fraction of vapour Dt : tm-tv, difference in time corresponding to Pm Pv V1 : Specific volume V0 : Vessel internal volume
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6.9. References :
Etchells, J.; Wilday, J. Workbook for chemical reactor relief system sizing, HSE Books, Contract research report 136/1998 Townsend, D.I.; Tou, J.C. Thermochimica Acta no 37, pp 1-30, 1980 Fisher, H.G. 5th DIERS Users Group Meeting Seattle, May 1989 Huff, J.E. Plant Operations Progress, Vol 1 no 4, pp 221-229, October 1992 Gustin, J.L. 6th Symp Loss Prevention and safety Promotion in the process Industry, Oslo Norway, June 19-22 1989, paper no 75 Fauske, H.C.; Leung, J.C. CEP August 1985, p10 Rogers, R.L. The advantages and limitations of adiabatic Dewar calorimetry in chemical hazard testing, International symposium on runaway reactions March 7-9, 1989 Cambridge Massachusetts, ppP 281-292 Fauske, H.K.; Clare, G.H.; Jo Creed, M. Laboratory tool for characterizing chemical systems Ibid p.364-371 Singh, J. PHI TEC: Enhanced vent sizing calorimeter application and comparison with existing devices, International symposium on runaway reactions, March 7-9 1989, Cambridge, Mass, USA (AIChE) Ottaway, M.R. Thermal hazard evaluation by accelerating rate calorimetry, analytical proc, 23:116, 1986 DIERS Reports : Bench scale ERS Sizing Tools : Equipment details and test procedures : FI/84-4, 1984 (AIChE, USA) Semenov, N.N. 1928, Z Phys Chem, 48/571. Frank Kamenetskii, DA, 1989, Diffusion and heat transfer in chemical Kinetics, 2nd edition (Plenum Press, London, UK). Barton, J.; Rogers, R. Chemical reaction hazards, IChemE. ISBN 0-85295-341-0 Leung, J.C. (1986), AIChE Journal, October 1986, Vol 32, no 10 Leung, J.C. (1987), AIChE Journal, June 1987, Vol 33, no 6 Singh, J. J. Loss Prevention in the Process Industries, 1994, Vol 7, no 6

6.adiabatic Calorimetry

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THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Volume 10 ml 100 ml 1000 ml 2,5 m3 5,0 m3 12,7 m3 1000 ml 25 m3

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Temprature en C Initial Temperatute=20,2C Final Temperature=165,2C Final pressure =14,8 bara

0 0 50 100 150 200

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Search Heat Wait Search

Search Heat Wait

0 0 2000 4000 6000 8000 10000 12000 14000 16000

Comparison Kinetic Adiabatic calorimeter / Pilot plant experiment

3 Laboratory test Pilot test 2

-2.6 -1000 / T (K)

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

6.4. Comparison of techniques and relative merit

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

So the classic kinetic expression: v = f (T ) g (a ) expressed assuming Arrhenius dependency

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Leung, J.C. (1987)

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Pressure Low f factor compensati on

Heat Wait Search

Closed cell test

Easy to Stirring use

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

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